Regioselective One-Pot Synthesis of Novel Functionalized Organoselenium Compound by Bis-Alkoxyselenenylation of Alkenes with Selenium Dibromide and Alcohols

Abstract

The one-pot efficient synthesis of novel functionalized organoselenium compound by bis-alkoxyselenenylation of alkenes with selenium dibromide and alcohols was developed. The reaction of the selenium dibromide with cyclopentene or cyclohexene in the system alcohol/sodium bicarbonate/methylene chloride at room temperature afforded bis(2-alkoxycycloalkyl) selenides in 90–99% yields. The regioselective and efficient method for bis-alkoxylation of terminal alkenes was developed based on the addition of selenium dibromide with 1-alkenes in acetonitrile followed by refluxing of addition products in alcohols in the presence of traces of sulfuric acid. This method made it possible to selectively obtain bis(2-alkoxyalkyl) selenides in 94–98% yields.

Recent Advances in Design and Synthesis of 1,3-Thiaselenolane and 1,3-Thiaselenole Derivatives

“…The first synthesis of organose-lenium compounds from selenium dichloride and dibromide is the preparation of 1,4selenasilafulvenes by the cyclization reaction of these reagents with dimethyldiethynylsilane [52]. The selectivity and efficiency of the use of selenium dichloride and dibromide in organic synthesis have been shown in many reactions, which made it possible to obtain previously unknown classes of organoselenium compounds and study their chemical properties [53][54][55][56][57][58][59][60][61][62][63][64][65][66]. Compounds with high glutathione peroxidase-like activity have been found [56].…”

“…A new methodology for the synthesis of fused heterocyclic selenium compounds is based on the annulation and annulation/functionalization reactions of selenium dihalides with aromatic and natural compounds [57,58]. Another general regioselective approach to new selenium-containing heterocyclic compounds is based on addition/bis-functionalization reactions of selenium dibromide with alkenes in the presence of nucleophilic reagents [59,60]. Using this approach, a one-pot synthesis of novel, functionalized organoselenium compounds by bis-alkoxyselenenylation of alkenes with selenium dibromide and alcohols has been developed [59].…”

“…Another general regioselective approach to new selenium-containing heterocyclic compounds is based on addition/bis-functionalization reactions of selenium dibromide with alkenes in the presence of nucleophilic reagents [59,60]. Using this approach, a one-pot synthesis of novel, functionalized organoselenium compounds by bis-alkoxyselenenylation of alkenes with selenium dibromide and alcohols has been developed [59]. An efficient regioselective synthesis of novel, functionalized organoselenium compounds by cyclofunctionalization reactions of selenium dihalides with natural compounds and their derivatives has also been realized [61].…”

“…The use of selenium dichloride and dibromide made it possible to discover new possibilities in organic synthesis [53][54][55][56][57][58][59][60][61][62][63][64][65][66]. The reaction of selenium dichloride with divinyl sulfide at −50 • C in chloroform gave six-membered heterocycle, 2,6-dichloro-1,4-thiaselenane (1) (a 6/1 diastereomer ratio), in quantitative yield, which underwent rearrangement (chloroform, room temperature) to a five-membered heterocycle, 5-chloro-2-chloromethyl-1,3thiaselenolane (2) in 61% yield (a 2/1 diastereomer ratio).…”

Transannular Selenocyclofunctionalization of 1,5-cyclooctadiene: The Antioxidant Properties of 9-selenabicyclo[3.3.1]nonane Derivatives and the Discovery of Increasing Both GPx and GR Activities

“…Seleniranium cations are postulated as intermediates in these reactions. Recently, we developed one-pot bis-alkoxyselenenylation of alkenes with selenium dibromide and alcohols [29]. This approach allows to realize one-pot selenobisfunctionalization reactions under mild conditions and to increase yields of the target products, avoiding the stage of the formation of the intermediate bis(β-halogenorganyl) selenides [29].…”